CN103476864A - Flame-retardant thermoplastic composition - Google Patents
Flame-retardant thermoplastic composition Download PDFInfo
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- CN103476864A CN103476864A CN201280009573XA CN201280009573A CN103476864A CN 103476864 A CN103476864 A CN 103476864A CN 201280009573X A CN201280009573X A CN 201280009573XA CN 201280009573 A CN201280009573 A CN 201280009573A CN 103476864 A CN103476864 A CN 103476864A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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Abstract
The invention relates to a thermoplastic composition comprising A) a polyalkylene terephthalate, B) an elastomer selected from the group b1) of polyalkylene terephthalate polyester urethanes, b2) of polyalkylene terephthalate polyether urethanes, C) a halogen-free flame retardant selected from the group c1) of nitrogen-containing flame retardants, c2) of nitrogen- and phosphorus-containing flame retardants, c3) of phosphorus-containing flame retardants selected from the group of phosphates, phosphine salts, diphosphine salts and mixtures thereof. The invention further relates to the use of the thermoplastic composition of the invention for producing fibres, foils or mouldings, and also to fibres, foils or mouldings which comprise the composition of the invention. The invention additionally relates to the use of the thermoplastic composition as coating material.
Description
The present invention relates to a kind of thermoplastic compounds, it comprises
A) poly terephthalic acid alkane diol ester (polyalkylene terephthalate)
B) be selected from the elastomerics of following material,
B1) poly terephthalic acid alkane diol ester PAUR,
B2) poly terephthalic acid alkane diol ester polyether(poly)urethane,
B3) poly terephthalic acid alkane diol ester polyethers,
B4) poly terephthalic acid alkane diol ester polyester,
And the mixture of these materials,
C) be selected from the halogen-free flame-retardant of following material,
C1) nitrogenous fire retardant,
C2) nitrogenous and phosphorous fire retardant,
C3) phosphorous fire retardant,
And the mixture of these materials.
The invention still further relates to the purposes of thermoplastic compounds of the present invention for the manufacture of fiber, paper tinsel or moulded product, and relate to fiber, paper tinsel or the moulded product that comprises the present composition.The invention still further relates to the purposes of described thermoplastic compounds as coating composition.
Particularly, the present invention relates to a kind of thermoplastic compounds, it comprises (A) polybutylene terephthalate, (B) polybutylene terephthalate PAUR (b1), (C) diethyl phospho acid aluminium, melamine cyanurate or polyphosphoric acid melamine, or the mixture of these materials.Another embodiment relates to a kind of thermoplastic compounds, it comprises (A) polybutylene terephthalate, (B) polybutylene terephthalate polyethers (b2), (C) diethyl phospho acid aluminium, melamine cyanurate or polyphosphoric acid melamine, or the mixture of these materials.
Particularly, the invention still further relates to a kind of thermoplastic compounds, it comprises (A) polybutylene terephthalate, (B) polybutylene terephthalate polyester (b3), (C) diethyl phospho acid aluminium, melamine cyanurate or polyphosphoric acid melamine, or the mixture of these materials.
Other preferred embodiments can be obtained by claim and specification sheets.The combination of preferred embodiment within the scope of the invention.
Demand to flame-retardant thermoplastic compositions more and more receives publicity, and particularly needs the composition of halogen, especially without chlorine with without the composition of bromine.
WO2009/009249A2 has described a kind of halogen polymer blend with various fire retardants and stabilization additives.Use conventional hard segment polyester in this invention.
US2008/0167406A1 has described a kind of Flameproof molding compounding based on polybutylene terephthalate, and it comprises thermoplastic polyester elastomer and phosphinates and epoxy compounds.On the one hand, described elastomerics can be the polyester-polyester elastomerics.The hard segment of this invention can be the polyester made by aromatic diacid and short chain aklylene glycol.Soft chain segment is comprised of polyester, aliphatic diacid and short chain aklylene glycol or polycaprolactone.On the other hand, described elastomerics can be polyester-polyether elastomer, wherein said hard segment is the polyester be comprised of aromatic diacid and short chain aklylene glycol, and described soft chain segment is poly suboxygen alkyl glycol or the polyester that made by poly suboxygen alkyl unit and aliphatic diacid.
WO2006/040066A1 has described a kind of Flameproof molding compounding, and it also comprises at least one highly branched or hyperbranched polycarbonate and/or polyester that at least one is highly branched or both mixtures except the polybutylene terephthalate as main ingredient.Can add various flame-retardant additives in moulding compound.
An object of the present invention is to develop a kind of thermoplastic compounds that there is good workability and there is fire retardation simultaneously.Another object of the present invention is to provide the composition with greyish white inherent colour.Another object of the present invention is the thermoplastic compounds that exploitation has fire retardation and smell neutrality.Described composition also is intended to be applicable to prepare coating.
Can realize described purpose with the thermoplastic compounds of describing in foreword.
The component A of thermoplastic compounds of the present invention is poly terephthalic acid alkane diol ester.This statement also comprises the mixture of poly terephthalic acid alkane diol ester.For the object of the invention, poly terephthalic acid alkane diol ester is not restricted to the compound that comprises terephthalate: contrary, poly terephthalic acid alkane diol ester of the present invention is derived from the structure that comprises the aromatic ring that is derived from aromatic dicarboxylic acid on main chain.Described aromatic ring can be the ring that does not replace or replace.Substituting group commonly used is in particular C
1-C
4alkyl group, for example methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-or the tertiary butyl or fluorine.
The dicarboxylic acid of preferred dicarboxylic acid for replacing, be in particular unsubstituted 2,6-naphthalene dicarboxylic acids, terephthalic acid and m-phthalic acid and composition thereof.Wherein, preferred terephthalic acid or m-phthalic acid or its mixture.Terephthalic acid is typically used as unique dicarboxylic acid monomer.
Except comprising the aromatics part derived from applicable dicarboxylic acid, poly terephthalic acid alkane diol ester also comprises the aliphatic hydrocrbon part derived from corresponding aklylene glycol.Described aklylene glycol can be branching or non-branching (linear).The hydrocarbon part that the poly terephthalic acid alkane diol ester of branching comprises branching, and the hydrocarbon part that linear poly terephthalic acid alkane diol ester comprises non-branching.Thermoplastic compounds of the present invention is preferably used linear poly terephthalic acid alkane diol ester.
In aklylene glycol, preferably there is the glycol of 2 to 6 carbon atoms, be in particular 1，2-ethandiol, 1, ammediol, BDO, 1,6-hexylene glycol, 1, the mixture of 4-hexylene glycol, Isosorbide-5-Nitrae-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanedimethanol or neopentyl glycol or these materials.
In a preferred embodiment of the present invention, component A can comprise polyethylene terephthalate, poly-1,3-propylene glycol ester terephthalate, poly-1, the mixture of 4-mutual-phenenyl two acid bromide two alcohol ester, PEN, poly-Isosorbide-5-Nitrae-naphthalic acid butanediol ester, poly-(terephthalic acid cyclohexanedimethanoester ester) or these materials.
The intrinsic viscosity that these poly terephthalic acid alkane diol esters are measured in phenol/tetracol phenixin (1/1 volume ratio) is generally 0.4dL/g to 2.0dL/g.The average molar mass of poly terephthalic acid alkane diol ester is generally 5000 to 130000g/mol (by gel permeation chromatography, (5/95 volume ratio) take polystyrene as the standard substance measurement in chloroform/hexafluoroisopropanol under 25 ℃).
Thermoplastic compounds of the present invention comprises a kind of elastomerics (B component), it is selected from poly terephthalic acid alkane diol ester PAUR b1), poly terephthalic acid alkane diol ester polyether(poly)urethane b2), poly terephthalic acid alkane diol ester polyethers b3), poly terephthalic acid alkane diol ester polyester b4) and the mixture of these materials.
Elastomerics is hard segment and the combinable multipolymer of soft chain segment wherein.Hard segment be take the rigid elongate sections usually as feature.Soft chain segment comprises the zone of obvious winding usually.The hard segment major part connects each other and forms inter-molecular linkage, and this has improved the coherency between polymer chain.Soft chain segment can be elongation, therefore for described zone, provides elasticity.
Elastomerics b1) comprise as the poly terephthalic acid alkane diol ester of hard segment with as the PAUR of soft chain segment (its molecular formula referring to WO03014179,9-10 page).
Preparation method commonly used---preferably uses one or more molar masss to be generally the low molecular weight diols (i) of 62g/mol to 500g/mol at this---with poly terephthalic acid alkane diol ester and one or more oxy-compound and reacts and starts to form poly terephthalic acid alkane diol ester oxy-compound.Subsequently described poly terephthalic acid alkane diol ester oxy-compound is first reacted with one or more polyesterols, the molar mass that described polyesterols has usually is 500 to 8000g/mol, preferably 700 to 6000g/mol, be in particular 800 to 4000g/mol (ii), and then from the mixture reaction (iii) of a kind of isocyanic ester or different isocyanic ester.
Described thermoplastic elastomer b1) hard segment can be different from poly terephthalic acid alkane diol ester A in structure forms and/or distributes.Yet hard segment also can have the structure identical with A and form.For example, the hard segment of described thermoplastic elastomer can be based on terephthalic acid and the poly terephthalic acid alkane diol ester with aklylene glycol of 2 to 15 carbon atoms.Preferred hard segment is polybutylene terephthalate, is in particular poly-Isosorbide-5-Nitrae-mutual-phenenyl two acid bromide two alcohol ester.The average molar mass of described poly terephthalic acid alkane diol ester fragment is generally 1000 to 5000g/mol (by gel permeation chromatography, (5/95 volume ratio) take polystyrene as the standard substance measurement in chloroform/hexafluoroisopropanol under 25 ℃).
In order to form poly terephthalic acid alkane diol ester oxy-compound, described thermoplastic poly terephthalic acid alkane diol ester can for example react with one or more glycol in step (i), preferably with well-known low molecular weight diols, react, the special glycol that is 62 to 500g/mol with mole molecular mass reacts, described glycol is for example ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, heptanediol, ethohexadiol, preferred BDO and/or 1，2-ethandiol.
In step (i), the weight ratio of poly terephthalic acid alkane diol ester and glycol is generally 100:1 to 100:10, preferably 100:1.5 to 100:8.0.Molar mass as the poly terephthalic acid alkane diol ester oxy-compound of the reaction product from (i) is preferably 1000g/mol to 5000g/mol.Fusing point as the poly terephthalic acid alkane diol ester oxy-compound of the reaction product from (i) is preferably 150 ℃ to 260 ℃, particularly preferably 151 ℃ to 260 ℃, be in particular 165 ℃ to 245 ℃, so this means in step (i) thermoplastic poly terephthalic acid alkane diol ester and reacts the poly terephthalic acid alkane diol ester oxy-compound obtained with glycol and comprise having above-mentioned fusing point and for the compound of following steps (ii).
At step I i) in, described poly terephthalic acid alkane diol ester oxy-compound can be for example 500 to 8000, preferably 700 to 6000 with molecular weight, be in particular 800 to 4000 aliphatic polyester alcohol reacts.The average functionality of polyesterols is preferably 1.8 to 2.6, and preferably 1.9 to 22, be in particular 2.Term " functionality " means the number of reactive hydrogen atom, particularly hydroxyl especially.
Preferably use can react with the hexanodioic acid as dicarboxylic acid the polyesterols obtained by the butyleneglycol as glycol and hexylene glycol, and wherein the weight ratio of butyleneglycol and hexylene glycol is preferably 2:1.The polytetrahydrofuran that preferably molar mass is 750 to 2500g/mol, preferably 750 to 1200g/mol in addition is as polyesterols.
According to thermoplastic poly terephthalic acid alkane diol ester in step (i) with glycol, react obtain poly terephthalic acid alkane diol ester oxy-compound and subsequently in step (ii) with the reacting of polyesterols, after step (iii) in will there is the free hydroxyl group group intermediate product with the further processing of isocyanic ester to obtain elastomerics b1)---poly terephthalic acid alkane diol ester PAUR.
The isocyanic ester used is generally conventional aliphatic series, alicyclic, the isocyanic ester of araliphatic and/or aromatics, preferred vulcabond, for example three, four, five, six, seven and/or eight methylene diisocyanates, 1,5-, bis-isocyanic acid 2-methyl five methylene esters, Isosorbide-5-Nitrae-bis-isocyanic acid 2-ethyl butylidene ester, 1,5-, bis-isocyanic acid five methylene esters, Isosorbide-5-Nitrae-bis-isocyanic acid Aden ester, 1-isocyanato-3,3, and 5-trimethylammonium-5-isocyanato methylcyclohexane (isophorone diisocyanate, IPDI), Isosorbide-5-Nitrae-and/or 1,3-bis-(isocyanato methyl) hexanaphthene (HXDI), hexanaphthene Isosorbide-5-Nitrae-vulcabond, 1-methylcyclohexane 2,4-and/or 2,6-vulcabond, dicyclohexyl methyl hydride 4,4 '-, 2,4 '-, and/or 2,2 '-vulcabond, ditan 2,2 '-, 2,4 '-and/or 4,4 '-vulcabond (MDI), naphthalene 1,5-vulcabond (NDI), toluene 2,4-and/or 2,6--vulcabond (TDI), diphenylmethanediisocyanate, 3,3 '-dimethyl diphenyl vulcabond, 1,2-diphenylethane vulcabond and/or phenylene vulcabond, preferred ditan 2,2 '-, 2,4 '-, and/or 4,4 '-vulcabond (MDI) and/or hexamethylene diisocyanate (HDI).
Suitable poly terephthalic acid alkane diol ester PAUR b1) example is the random distribution multipolymer that soft segment content is 10 % by weight to 35 % by weight.
Can be prepared by known method by those skilled in the art by described poly terephthalic acid alkane diol ester PAUR, for example in forcing machine, synthesize in batches or react to prepare.
The described thermoplastic elastomer b1 formed by hard segment and soft chain segment) a feasible synthetic WO03014179 of being recorded in (the 7th page, the 32nd walks to the 8th page, the 42nd row, the 13rd to 18 pages).
Described elastomerics b2) comprise as the poly terephthalic acid alkane diol ester of hard segment with as the polyether(poly)urethane of soft chain segment.For this reason, poly terephthalic acid alkane diol ester oxy-compound as above can react with one or more Aethoxy Sklerols.The molar mass that these Aethoxy Sklerols have usually is 500g/mol to 8000g/mol, and preferably 700 to 6000g/mol, is in particular 800 to 4000g/mol.The preferred average functionality of described Aethoxy Sklerol is 1.8 to 2.6, preferably 1.9 to 2.2, be in particular 2.
According to thermoplastic poly terephthalic acid alkane diol ester in step (i) with glycol, react generate poly terephthalic acid alkane diol ester oxy-compound and subsequently in step (ii) with the reacting of Aethoxy Sklerol, after step (iii) in will there is the free hydroxyl group group intermediate product with the further processing of isocyanic ester to obtain actual product---poly terephthalic acid alkane diol ester polyether(poly)urethane.Carry out as mentioned above this and react to prepare elastomerics b1).
Suitable poly terephthalic acid alkane diol ester polyether(poly)urethane b2) example is the random distribution multipolymer that soft segment content is 10 % by weight to 35 % by weight.
Can, by those skilled in the art by known method preparation, for example in forcing machine, by synthesize or react in batches, prepare by described poly terephthalic acid alkane diol ester polyether(poly)urethane.
In another embodiment of the invention, described thermoplastic compounds comprises the elastomerics b3 that contains poly terephthalic acid alkane diol ester polyethers).Such product is knownly in document maybe can obtain by known method itself.For example, the polyester polyethers is recorded in following United States specification: 3,651,014,3,784,520,4,185,003 and 4,136,090.
Described elastomerics b3) hard segment can be different from poly terephthalic acid alkane diol ester A on structure forms and/or distributes.Yet described hard segment also can have the structure identical with A and form.For example, the hard segment of described thermoplastic elastomer can be the polyester based on terephthalic acid and the aklylene glycol based on having 2 to 15 carbon atoms.Described hard segment is preferably polybutylene terephthalate.
The soft polyether segment of the thermoplastic elastomer in the present invention (b2) can be the polyester polyethers.In the present invention, statement polyester polyethers means the compound of derivative autohemagglutination (alkylidene group) ether glycol and the low-molecular-weight glycol of short chain and dicarboxylic acid.
It is capable that feasible structural formula is recorded in the WO2007/009930 specification sheets the 29th page of 1-15.Certainly also can use multiple poly-(alkylene oxide) glycol, multiple glycol/or the mixture of multiple dicarboxylic acid.
The fusing point of poly-(alkylene oxide) glycol preferably is preferably 2 to 10, is in particular 2 to 6 lower than 55 ℃ and its carbon had/oxygen ratio.The example of poly-(alkylene oxide) glycol has poly-(ethylene oxide) glycol, poly-(1, the 2-propylene oxide) glycol, poly-(1, the 3-propylene oxide) glycol, poly-(1, the 2-oxybutylene) glycol, poly-(1, the 3-oxybutylene) glycol, poly-(1, the 4-oxybutylene) glycol, poly-(pentamethylene oxygen) glycol, poly-(hexa-methylene oxygen) glycol, poly-(heptamethylene oxygen) glycol, poly-(1, the octylene oxygen of 8-) glycol, poly-(1, random or the segmented copolymer of the nonamethylene oxygen of 9-) glycol, and above-mentioned those various polyvalent alcohols.Preferably use the mixture of poly-(ethylene oxide) glycol, poly-(1,2-propylene oxide) glycol, poly-(1,3-propylene oxide) glycol and poly-(Isosorbide-5-Nitrae-oxybutylene) glycol and these materials.The molar mass of poly-(alkylene oxide) glycol of long-chain can be preferably 400 to 3000g/mol.Molar mass can be determined by the OH number.For this reason, can establish the OH number by volumetry.Molar mass Mw thereby can measure (Carey, M. by using the OH number in formula Mw ≈ 56.1 * functionality * 1000/1mg KOH/g; Wellons, S.; Elder, D.Journal of Cellular Plastics1984,20,42.).
Spendable glycol is generally molecular weight preferably lower than 250 low molecular weight diols.The precursor structure of these glycol can be linearity or branching, cyclic aliphatic or aromatics.
The glycol that particularly preferably there are 2 to 15 carbon atoms.The example that can mention at this has 1，2-ethandiol, 1,3-PD, 1,2-PD, BDO, 1,3 butylene glycol, 1,2-butyleneglycol, 1,5-PD, 2，2-dimethyl-1，3-propanediol, 1,6-hexylene glycol and isomer thereof.Wherein, particularly preferably there are 2 to 8, be in particular the aliphatic diol of 2 to 4 carbon atoms, be in particular 1,3-PD and/or BDO.Verified undersaturated glycol is also applicable, special when mixing with above-mentioned glycol.But at this lay special stress on 2-butylene-Isosorbide-5-Nitrae--glycol.
Available dicarboxylic acid is preferably molecular weight at the compound below 300.Described dicarboxylic acid can be aromatics, aliphatic series or alicyclic compound, and can have the substituting group that does not produce interference in polymerization process.As long as the polymkeric substance of gained can be soft chain segment, described dicarboxylic acid also can be aromatic substance, and can have substituting group.
The example of the aromatic dicarboxylic acid that can mention has terephthalic acid, m-phthalic acid and composition thereof.Available aliphatic dicarboxylic acid has oxalic acid, fumaric acid, toxilic acid, citraconic acid, sebacic acid, hexanodioic acid, pentanedioic acid, succsinic acid, nonane diacid etc.Also can use the mixture of various aliphatic dicarboxylic acids.Except described acid, the ester derivative that also can use these acid to form.Preferred aromatic dicarboxylic acid.The feasible synthetic US3651014 that is recorded in of described thermoplastic elastomer (b2).
Various segmented copolymers are suitable for use as poly terephthalic acid alkane diol ester polyethers b3).
In another embodiment of the invention, described thermoplastic compounds comprises the elastomerics b4 that can be poly terephthalic acid alkane diol ester polyester).
B4) thereby can be the multipolymer of the mixture that comprises aromatic diacid and aliphatic diacid, wherein glycol is added in mixture.
Described aromatic diacid can be 2,6-naphthalene dicarboxylic acids, terephthalic acid and m-phthalic acid or these sour mixtures.
Described aliphatic dicarboxylic acid can be oxalic acid, fumaric acid, toxilic acid, citraconic acid, sebacic acid, hexanodioic acid, pentanedioic acid, succsinic acid, nonane diacid or these sour mixtures.
Described glycol can be the C2-C15-glycol, for example 1，2-ethandiol, 1,3-PD, 1,2-PD, BDO, 1,3 butylene glycol, 1,2-butyleneglycol, 1,5-PD, 2，2-dimethyl-1，3-propanediol, 1,6-hexylene glycol and isomer thereof.
The mol ratio of aromatic diacid and aliphatic diacid can from 9/1 to 1/9 varies widely.
Can, by those skilled in the art by known method preparation, for example in forcing machine, by synthesize or react in batches, prepare by described poly terephthalic acid alkane diol ester polyester.
Thermoplastic compounds of the present invention also comprises the fire retardant (C) of halogen, the fire retardant that it is selected from halogen-containing or phosphorous fire retardant or contains P and contain N, and the mixture of these materials.
About this point, term " halogen " should according to " International Electrotechnical Commission " (IEC61249-2-21) and " Japanese printed wiring employer's organization " definition of (JPCA-ES-01-1999) providing explain, it is defined as essentially no chlorine by halogen-free material and without those materials of bromine.
Described thermoplastic compounds can comprise and being selected from containing nitrogen combustion inhibitor (c1)---a kind of halogen compound of the nitrogenous heterocycle from thering is at least one nitrogen-atoms.Described thermoplastic compounds also can comprise the nitrogenous heterocyclic mixture with at least one nitrogen-atoms.
In the present invention, preferred applicable fire retardant is melamine cyanurate.The reaction product of the trimeric cyanamide that melamine cyanurate is preferred equimolar amount (formula I) and cyanuric acid or tricarbimide (formula Ia and Ib)
The isocyanic acid trimeric cyanamide can obtain by for example reaction of the aqueous solution under 90 to 100 ℃ through initial compounds.
Other suitable compounds (also often being known as salt or adducts) are trimeric cyanamide, melamine borate salt and trimeric cyanamide oxalate.Also can use the mixture of described salt.
In fire retardant (C), thermoplastic compounds of the present invention also can comprise to come self-contained P and contain the halogen compound of N fire retardant (c2).Suitable containing P and containing the case history of N fire retardant in
At this, suitable compound has melamine phosphate (one-level), melamine phosphate (secondary) and melamine pyrophosphate (secondary), trimeric cyanamide neopentyl glycol boric acid ester and polyphosphoric acid melamine (No. CAS: 56386-64-2)
Suitable guanidinesalt is
No. CAS
For the purposes of the present invention, described compound comprises for example benzoguanamine itself and adducts or salt, and the derivative replaced on nitrogen and adducts or salt.
Another suitable compound is ammonium polyphosphate (NH
4pO
3)
n, wherein n is about 200 to 1000, and preferably 600 to 800, and three (hydroxyethyl) chlorinated isocyanurates (THEIC) of formula II
The benzoguanamine compound that other suitable compounds are formula III
R wherein
9and R
10for the moieties of straight or branched with 1 to 10 carbon atom, preferably hydrogen, be in particular the adducts with phosphoric acid, boric acid and/or tetra-sodium.
The also salt of the wallantoin compound of preferred formula IV and these compounds and phosphoric acid, boric acid and/or tetra-sodium, and the glycoluril of formula V and with the salt of above-mentioned acid,
R wherein
9and R
10as definition as described in formula III,
R wherein
9as definition as described in formula III.
Suitable product is commercially availablely to obtain or can obtain according to for example DE-A19614424.
The dicyanodiamide that the present invention can use (formula VI) can be by for example obtaining with reacting of carbonic acid through calcium cyanamide, and the cyanamide dipolymer wherein generated is to form dicyanodiamide at 9 to 10 o'clock at pH.
Phosphinates and/or the phosphinates of formula (VIII) and/or their polymkeric substance that preferred P contained compound (c3) is formula (VII).
Can mention some examples from more substantial the present invention applicable P contained compound.
Substituent being defined as follows wherein:
R
11and R
12c for hydrogen, linearity or branching
1-C
6alkyl, preferably C
1-C
4alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl; Phenyl; Preferred at least one part R wherein
11or R
12for hydrogen and particularly R
11and R
12be hydrogen;
R
13for linearity or C branching
1-C
10-alkylidene group, for example methylene radical, ethylidene, positive propylidene, isopropylidene, positive butylidene, tertiary butylidene, positive pentylidene, just octylene, positive inferior dodecyl;
Arylidene, for example phenylene, naphthylidene;
Alkyl arylene, for example methylphenylene, ethyl phenylene, tertiary butyl phenylene, methyl naphthylidene, ethyl naphthylidene, tertiary butyl naphthylidene;
Aryl alkylene, for example phenylmethylene, phenyl ethylidene, phenyl propylidene, phenyl butylidene;
M is alkaline-earth metal or basic metal, Al, Zn, Fe, Mg, Ca;
The integer that s is 1 to 3;
The integer that z is 1 to 3, and
X is 1 or 2.
The particularly preferably compound of formula VII, wherein R
11and R
12for hydrogen, methyl, ethyl or isobutyl-, the wherein preferred Ca of M, Zn, Mg or Al, and the utmost point particularly preferably diethyl phospho acid aluminium and phospho acid aluminium.
The phosphorus of valence state+0 is element phosphor.Can use red phosphorus and black phosphorus.Preferred red phosphorus.
The phosphorus compound that spendable oxidation state is+5 is in particular the phosphoric acid ester of alkyl and aryl replacement.The example has the two 1-isobutyl-3,5-dimethylhexylphosphoric acids of phenyl, phenylethyl phosphoric acid hydrogen ester, phenyl two (3,5,5-trimethylammonium hexyl) phosphoric acid ester, ethyl-2-phenyl-phosphate, 2-ethylhexyl xylyl phosphoric acid ester, diphenylphosphoric acid hydrogen ester, two (2-ethylhexyl) p-methylphenyl phosphoric acid ester, trimethylphenyl phosphoric acid ester, two (2-ethylhexyl) phenyl phosphate ester, dinonyl phenyl phosphate ester, phenyl methyl phosphoric acid hydrogen ester, two dodecyl p-methylphenyl phosphoric acid ester, p-methylphenyl two (2,5,5-trimethylammonium hexyl) phosphoric acid ester and 2-ethylhexyl diphenyl phosphate.Specially suitable phosphorus compound is that wherein each part is aryloxy those compounds partly.Its cyclosubstituted derivative that extremely specially suitable compound is triphenylphosphate and/or Resorcinol two (diphenyl phosphate) and/or general formula X (RDP):
Substituent being defined as follows wherein:
R
18-R
21for thering is the aromatics part of 6 to 20 carbon atoms, preferred phenyl moiety, the alkyl group (preferable methyl) that described aromatics part can be had 1 to 4 carbon atom replaces,
R
22for the divalent phenol part, preferably
And the mean value of n is 0.1 to 100, preferably 0.5 to 50, be in particular 0.8 to 10, and the utmost point is in particular 1 to 5.
Because it prepares the method for using, current commercially available RDP product be approximately 85% RDP (n=1) and about 2.5% triphenylphosphate and approximately 12.5% wherein oligomerization degree great majority be less than the mixture of 10 oligomeric fragment.
Thermoplastic compounds of the present invention can comprise the enhancement additive (D) of fibrous, spherical and/or stratiform.Described enhancement additive can be glass fibre for example, carbon fiber, Kevlar, potassium titanate fiber, granulated glass sphere, soft silica, Calucium Silicate powder, magnesiumcarbonate, kaolin, chalk, silica powder, mica, barium sulfate, feldspar, metal hydroxides, metal oxide, similar mineral filler or pottery.The mixture of enhancement additive is also feasible.
Thermoplastic compounds of the present invention also can comprise at least one and add material, and described material is selected from stablizer, static inhibitor, nucleator, processing aid, impact modifying agent, lubricant and demolding aids, pigment and antioxidant.
The example of available UV stablizer for the Resorcinol that replaces, salicylate, benzotriazole category and benzophenone.
The example of suitable mineral dye has titanium dioxide, ultramarine and/or carbon black, but and the example of the pigment dyestuff of blending has perylene, phthalocyanine and/or quinacridone.Other suitable materials have dyestuff, for example, for nigrosine and/or anthraquinone by described thermoplastic compounds dyeing.
Available lubricant and releasing agent have longer chain fatty acid (for example stearic acid) or its salt (for example calcium stearate).The lubricant used and releasing agent weight ratio be usually up to 1%, the integral body meter based on thermoplastic compounds.
Available concrete softening agent is dioctyl phthalate (DOP), dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon ils and/or N-(normal-butyl) benzsulfamide.
Thermoplastic compounds of the present invention can comprise fluorine-containing ethene polymers.It preferably includes the ethene polymers that fluorine content is 55 to 76 % by weight.Example herein tetrafluoroethylene (PTFE) is arranged but, tetrafluoraoethylene-hexafluoropropylene copolymer and the TFE copolymer of ethylenically unsaturated monomers with copolymerization of relative small proportion.These are described in " Vinyl and Related Polymers " by for example Schildknecht, and Wiley-Verlag, in 1952, the 484 to 494 pages.
Described additive can join in a kind of component or join in thermoplastic compounds integral body with the form of independent blend by blend.
Composition of the present invention preferably includes not fluorine-containing ethene polymers.
Add material in the situation that composition of the present invention comprises one or more, the ratio of these materials is not usually higher than 5 % by weight, based on the whole meter of thermoplastic compounds.The ratio of adding material is at least 0.1 % by weight usually, based on the whole meter of thermoplastic compounds.
Component (A), (B), (C) and (D) can mix by various part by weight.Below relate to the data of weight percent based on the whole meter of thermoplastic compounds.Single weight percent in thermoplastic compounds and be 100 % by weight.
For example, composition of the present invention comprises 30 to 70 % by weight components (A), based on the whole meter of thermoplastic compounds.The part by weight of available (A) is preferably 40 to 60 % by weight, is in particular 40 to 55 % by weight, based on the whole meter of thermoplastic compounds.
The usage quantity of thermoplastic elastomer (B) is 1 to 50 % by weight.The preferred usage quantity of thermoplastic elastomer is 1 to 30 % by weight, is in particular 3 to 15%, based on the whole meter of thermoplastic compounds.
Can add the halogen-free flame-retardant (C) that part by weight is 5 to 35 % by weight, based on the whole meter of thermoplastic compounds, described halogen-free flame-retardant (C) is selected from c1) containing nitrogen combustion inhibitor, c2) nitrogenous and phosphorous fire retardant or c3) phosphonium flame retardant, and the mixture of these materials.Preferably to add part by weight be 5 to 30 % by weight, be in particular the fire retardant of 5 to 25 % by weight.
In the situation that material comprises enhancement additive (D), its available part by weight is 1 to 50 % by weight, based on the whole meter of thermoplastic compounds.In a preferred embodiment, the enhancement additive that it is 15 to 60 % by weight that described thermoplastic compounds comprises part by weight, be in particular 15 to 30 % by weight, based on the whole meter of thermoplastic compounds.
Following composition is the preferred thermoplastic compounds of the present invention.
A: each weight percent in thermoplastic compounds and be 100 % by weight.Each thermoplastic compounds also can comprise the interpolation material.
Thermoplastic compounds of the present invention can be by known method preparation.For this reason, for example for example, in conventional mixing device (forcing machine based on screw rod, Brabender mixing tank or Banbury mixing tank), mix starting ingredient, subsequently it is extruded, extrudate can be cooled and pulverize.Also can be by single component premix, and subsequently all the other parent materials single and/or that also can be the form of mixing are added in mixture.Mixing temperature is generally 240 ℃ to 265 ℃.The temperature of temperature based on forcing machine.
The mechanical property of thermoplastic compounds of the present invention is conducive to described thermoplastic compounds is used for manufacturing fiber, paper tinsel and/or moulded product.Described thermoplastic compounds is specially adapted to manufacture the certain molded articles in the structure of automobile and equipment, for example, for industry or the relevant purpose of consumption.Therefore, described thermoplastic compounds can be used for manufacturing electronic package, house, house parts, protective cover plate, collision bumper, interceptor, car body component, damping element, spring, handle, charge air duct (charge-air pipe), motor vehicle interiors application, for example dashboard, instrument panel assembly, supporting part for instrument panel, shield cap, inlet pipe, air-inlet grille, skylight guide rail (sunroof rail), roof stick carline, add-on assemble, particularly as the central control station of the part of glove box, or velocity gauge lid.
Thermoplastic compounds of the present invention can be used as the coating composition of fiber, paper tinsel and/or moulded product.The term moulded product means following goods: it is that three-dimensional solid and its can easily apply to obtain with thermoplastic compounds.The thickness of these coatings is generally 0.1 to 3.0cm, and preferably 0.1 to 2.0cm, and the utmost point is particularly preferably 0.5 to 2.0cm.This type coating can be by those skilled in the art by known method preparation.
Thermoplastic compounds of the present invention can be used in the preparation process of flame retardant materials of industrial production.
Thermoplastic compounds of the present invention presents the fire retardation that meets the strictest requirement.In order to prove flame-retarding characteristic, manufactured moulded product, and unexpectedly, in view of the good workability of these moulded products, it has passed through the UL94 combustion test that grade is V-0 or V-2.
Described thermoplastic compounds has unexpectedly favourable melt flow index and higher resistance to breakage and shock-resistance.
The material used:
Component A:
PTB1: poly-(mutual-phenenyl two acid bromide two alcohol ester) that fixedly viscosity is 130mL/g (being measured in the phenol/orthodichlorobenzene that is 0.5 % by weight in concentration under 23 ℃ (1/1) mixture), purchased from BASF SE's
b4520.
PBT2: there is poly-(mutual-phenenyl two acid bromide two alcohol ester) that fixedly viscosity is 107mL/g (being measured in the phenol/orthodichlorobenzene that is 0.5 % by weight in concentration (1/1) mixture) under 23 ℃, purchased from BASF SE's
b2520.
B component:
Components b 1)
Polyethylene terephthalate polyester type polyurethane 1-3: comprise poly-(mutual-phenenyl two acid bromide two alcohol ester), adipic acid ester, two isocyanic acid six methylene ester and butyleneglycols; Hardness and melt index (entire body flow index (MFI) in Table.
Polyethylene terephthalate polyester type polyurethane 1
PBT：60％
Polyvalent alcohol: 25% polyester, it is made by hexanodioic acid, butyleneglycol and 2-methyl propanediol (1+1), Mn=3000g/mol; OH value: 38mg KOH/g
Isocyanic ester: 9% two isocyanic acid six methylene esters
BDO: 3.6%
Additive (talcum of fine powdered, the sterically hindered phenol as antioxidant, the carbodiimide as hydrolysis stabilizer, slip additive, antiblocking agent): 3.4%
Polyethylene terephthalate polyester type polyurethane 2
PBT：67.5％
Polyvalent alcohol: 16% polyester, it is made by hexanodioic acid, butyleneglycol and 2-methyl propanediol (1+1), Mn=3000g/mol; OH value: 38mg KOH/g
Isocyanic ester: 9% two isocyanic acid hexa-methylene esters
BDO: 4.1%
Additive (talcum of fine powdered, the sterically hindered phenol as antioxidant, the carbodiimide as hydrolysis stabilizer, slip additive, antiblocking agent): 3.4%
Polyethylene terephthalate polyester type polyurethane 3
PBT：71％
Polyvalent alcohol: 12.6% polyester, it is made by hexanodioic acid, butyleneglycol and 2-methyl propanediol (1+1), Mn=3000g/mol; OH value: 38mg KOH/g
Isocyanic ester: 9% two isocyanic acid hexa-methylene esters
BDO: 4.3%
Additive (talcum of fine powdered, the sterically hindered phenol as antioxidant, the carbodiimide as hydrolysis stabilizer, slip additive, antiblocking agent): 3.1%
Components b 3)
Polyethylene terephthalate polyethers 1 and 2: comprise poly-(mutual-phenenyl two acid bromide two alcohol ester) and polytetrahydrofuran;
7246 Hes
8238, purchased from DuPont, hardness and melt index (entire body flow index (MFI)) in Table.
Components b 4)
Polyethylene terephthalate polyester: comprise poly-(mutual-phenenyl two acid bromide two alcohol ester) and poly-hexanodioic acid fourth diester; Purchased from BASF SE's
fBX7011, hardness and melt index (entire body flow index (MFI)) in Table.
Component C:
DEPAL: diphosphinic acid aluminium triethyl.
MC: melamine cyanurate, purchased from BASF SE's
mC25.
MPP: polyphosphoric acid melamine, purchased from BASF SE's
200.
Component D:
Glass fibre: PPG3786 glass fibre
Other add material:
Stablizer: stablizer comprises various antioxidants: main phenol antioxidant and less important antioxidant, for example phosphorous acid ester and sulfo-synergistic agent): purchased from the Irganox1010 of BASF SE.
Lubricant: oxidized polyethlene wax, purchased from BASF SE's
oA5.
The preparation of thermoplastic compounds, processing and test:
At 260 times, each mixture is mixed in twin screw extruder also subsequently according to ISO294 (title: the injection moulding of the test sample book of plastics-thermoplastic material) by its injection moulding.
Use the sample measurement melt volume flow rate (MVR) of 2.16kg weight under 275 ℃.
The mensuration of tensile property) and ISO179 (title: the summer is than the mensuration of (charpy) impact property) carries out tensile strength test and notch shock is tested according to ISO527 (title:.
The sample that is 0.8mm or 1.6mm with 5 thickness carries out the flammable UL94 test of plastics.
The required pressure of sample of the 0.8mm thickness of injection moulding pressure based on for the preparation of the flammable UL94 test of plastics.
Embodiment: poly terephthalic acid alkane diol ester PAUR+DEPAL+MC
With the comparative example, compare, sample demonstrates the mechanical property of improvement and the fire retarding effect of improvement (comparative example and particularly inventive embodiments 2).
Polyphosphoric acid melamine add the further fire retarding effect (inventive embodiments 3 and particularly inventive embodiments 7) that improved.In addition, Compound Phase is compared to the comparative example and has demonstrated the mechanical property of improving, and particularly, in Impact Test, thermoplastic compounds presents the anti-Charpy impact (comparative example and particularly inventive embodiments 9) of improvement.
In another embodiment, the mixture of preparation comprises PBT, diethyl phospho acid aluminium (DEPAL), melamine cyanurate, poly terephthalic acid alkane diol ester polyethers 1 separately or poly terephthalic acid alkylidene group polyethers 2 and purchased from stablizer Irganox1010 and the PPG3786 glass fibre of BASF.Change respectively poly terephthalic acid alkane diol ester polyethers 1 and quantitative ratio poly terephthalic acid alkane diol ester polyethers 2.
With the comparative example, compare, sample demonstrates the mechanical property of improvement and the fire retarding effect of improvement (comparative example and particularly inventive embodiments 11).
In another embodiment, polyphosphoric acid melamine is added in described mixture, this has further improved fire retarding effect (inventive embodiments 12 and particularly inventive embodiments 15).In addition, Compound Phase is compared to the mechanical property that the comparative example presents improvement, and particularly in Impact Test, thermoplastic compounds presents the anti-Charpy impact (comparative example and particularly inventive embodiments 17 and 18) of improvement.
In another embodiment, the mixture of preparation comprises PBT, diethyl phospho acid aluminium (DEPAL), melamine cyanurate, polyphosphoric acid melamine and poly terephthalic acid alkane diol ester polyester (poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-(tetramethylene adipate)) and purchased from stablizer Irganox1010 and the PPG3786 glass fibre of BASF.Changed the quantitative ratio of poly terephthalic acid alkane diol ester polyester.
With the comparative example, compare, sample demonstrates the mechanical property of improvement and the fire retarding effect of improvement (comparative example and particularly inventive embodiments 19 and 20).
In inventing all embodiment, with the comparative example, compare, changed the mobility value by adding poly terephthalic acid alkane diol ester PAUR 1,2,3, poly terephthalic acid alkane diol ester polyethers 1,2, poly terephthalic acid alkane diol ester polyester.
Claims (10)
1. the present invention relates to a kind of thermoplastic compounds, it comprises
A) poly terephthalic acid alkane diol ester
B) be selected from the elastomerics of following material
B1) poly terephthalic acid alkane diol ester PAUR,
B2) poly terephthalic acid alkane diol ester polyether(poly)urethane,
And the mixture of these materials,
C) be selected from the halogen-free flame-retardant of following material,
C1) nitrogenous fire retardant,
C2) nitrogenous and phosphorous fire retardant,
C3) be selected from the phosphorous fire retardant of the mixture of phosphoric acid salt, phosphinates and diphosphinic acid salt and these materials.
2. according to the thermoplastic compounds of claim 1, b1 wherein) be the polybutylene terephthalate PAUR.
3. according to the thermoplastic compounds of any one in aforementioned claim, c1 wherein) for thering is the nitrogen heterocyclic ring of at least one nitrogen-atoms.
4. comprise (D) enhancement additive according to the thermoplastic compounds of any one in aforementioned claim.
5. according to the thermoplastic compounds of any one in aforementioned claim, the mixture that it comprises (A) polybutylene terephthalate, (B) polybutylene terephthalate PAUR (b1), (C) diethyl phospho acid aluminium, melamine cyanurate or polyphosphoric acid melamine or these materials.
6. according to the thermoplastic compounds of any one in aforementioned claim, the mixture that it comprises (A) polybutylene terephthalate, (B) polybutylene terephthalate polyethers (b3), (C) diethyl phospho acid aluminium, melamine cyanurate or polyphosphoric acid melamine or these materials.
7. according to the thermoplastic compounds of any one in aforementioned claim, the mixture that it comprises (A) polybutylene terephthalate, (B) polybutylene terephthalate polyester (b4), (C) diethyl phospho acid aluminium, melamine cyanurate or polyphosphoric acid melamine or these materials.
8. the purposes as coating composition according to the thermoplastic compounds of any one in aforementioned claim.
9. the purposes for the preparation of fiber, paper tinsel or moulded product according to the thermoplastic compounds of any one in claim 1 to 9.
10. a fiber, paper tinsel or moulded product, the thermoplastic compounds that it comprises any one in claim 1 to 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11151122A EP2476730A1 (en) | 2011-01-17 | 2011-01-17 | Flame-retardant thermoplastic compound |
| EP11151122.6 | 2011-01-17 | ||
| PCT/EP2012/050332 WO2012098035A1 (en) | 2011-01-17 | 2012-01-11 | Flame-retardant thermoplastic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103476864A true CN103476864A (en) | 2013-12-25 |
Family
ID=44141027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280009573XA Pending CN103476864A (en) | 2011-01-17 | 2012-01-11 | Flame-retardant thermoplastic composition |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20130310494A1 (en) |
| EP (2) | EP2476730A1 (en) |
| KR (1) | KR20140007816A (en) |
| CN (1) | CN103476864A (en) |
| BR (1) | BR112013017962A2 (en) |
| WO (1) | WO2012098035A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107429020A (en) * | 2015-12-03 | 2017-12-01 | 株式会社Lg化学 | Halogen thermoplastic resin composition and the cable for including it |
| CN112313273A (en) * | 2018-06-25 | 2021-02-02 | 巴斯夫欧洲公司 | Flame retardant thermoplastic polyurethanes |
| CN112812366A (en) * | 2020-12-30 | 2021-05-18 | 浙江新化化工股份有限公司 | Flame-retardant composition and application thereof, PBT composite material and preparation method thereof |
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| US8987357B2 (en) | 2011-05-27 | 2015-03-24 | Basf Se | Thermoplastic molding composition |
| KR102259248B1 (en) * | 2013-04-29 | 2021-06-01 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | Halogen-free flame retardant tpu |
| KR20170032731A (en) | 2015-09-15 | 2017-03-23 | 한국건설기술연구원 | A Fabric sheet of Fire Protection using Waved Profile of high temperature maintained shape |
| KR20170032727A (en) | 2015-09-15 | 2017-03-23 | 한국건설기술연구원 | A Fire Protection System Using Waved Profile of High Temperature Maintained Shape |
| KR20170032738A (en) | 2015-09-15 | 2017-03-23 | 한국건설기술연구원 | A Fire Protection Duct System and Constructing Method Using Waved Profile of High Temperature Maintained Shape |
| KR20170032744A (en) | 2015-09-15 | 2017-03-23 | 한국건설기술연구원 | A Fire Protection Cover of Electric Contact and Constructing Method Using Waved Profile of High Temperature Maintained Shape |
| WO2017063841A1 (en) | 2015-10-14 | 2017-04-20 | Basf Se | Polyester blend having a halogen-free flame protection |
| JP6737679B2 (en) * | 2016-09-30 | 2020-08-12 | アイカ工業株式会社 | Flame-retardant resin composition |
| WO2018210608A1 (en) * | 2017-05-17 | 2018-11-22 | Basf Se | Impact resistant polymer mixture |
| WO2021224136A1 (en) | 2020-05-06 | 2021-11-11 | Basf Se | Flame retarded polyester blend |
| TW202313845A (en) * | 2021-09-16 | 2023-04-01 | 廣鑫複合材料股份有限公司 | Thermoplastic polyurethane composition, and dyeable fiber made therefrom and method for preparing the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20130310494A1 (en) | 2013-11-21 |
| WO2012098035A1 (en) | 2012-07-26 |
| EP2665773A1 (en) | 2013-11-27 |
| EP2476730A1 (en) | 2012-07-18 |
| BR112013017962A2 (en) | 2019-09-24 |
| KR20140007816A (en) | 2014-01-20 |
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Application publication date: 20131225 |